Photosensitive compositions comprising 1,1-disubstituted-1,2-dihydro-2,4-disubstituted phthalazines

ABSTRACT

WHERE A completes a fused, mono or polynuclear aromatic ring, having 6 to 10 carbon atoms; X is a member selected from the group consisting of chloro, lower alkyl, having from 1 to 4 carbon atoms, and phenyl; l is a positive integer from 1 to 3; R1 and R2 are the same or different members selected from the group consisting of alkyl, having from 1 to 8 carbon atoms, phenyl, naphthyl and benzyl; R3 is a phenyl or 1-naphthyl group; Y is a member selected from the group consisting of dimethylamino and methoxy; m is an integer from 0 to 1; R4 is a phenyl or naphthyl group; Z is a 4-nitro group; and n is an integer from 0 to 1.   The 1,1-disubstituted-1,2-dihydro-2,4-disubstituted-phthalazine compounds of Formula I are converted to the azomethineimine dyes of Formula II by irradiation with ultraviolet light. The conversion is useful in photographic processes.

United States Patent [72] Inventor Balwant Singh Stamford, Conn.

[21] Appl. No. 14,240

[22] Filed Feb. 25, 1970 [45] Patented Jan. 11, 1972 [73] AssigneeAmerican Cyanamid Company Stamford, Conn.

[54] PHOTOSENSITIVE COMPOSITIONS COMPRISINGl,l-DISUBSTITUTED-l,2-DIHYDRO-2,4- DISUBSTITUTED PHTHALAZINES 6 Claims,No Drawings [52] US. Cl 96/48,

[51] Int. Cl G03c 5/24,

[50] Field of Search 96/48, 90

[56] References Cited UNITED STATES PATENTS 3,446,648 5/l969 Workman96/48 3,351,467 ll/l967 Sprague 96/90 Primary ExaminerNorman G. TorchinAssistant ExaminerRichard E. F ichter Attorney-Robert Raymond ABSTRACT:The l, l -disubstituted-l ,2-dihydro-2,4-disubstituted-phthalazinecompounds of Formula I are converted to the azomethineimine dyes ofFormula ll by irradiation with ultraviolet light. The conversion isuseful in photographic processes.

where A completes a fused, mono or polynuclear aromatic ring, having 6to ID carbon atoms; X is a member selected from the group consistingofchloro, lower alkyl, having from I to 4 carbon atoms, and phenyl; [isa positive integer from l to 3; R and R are the same or differentmembers selected from the group consisting of alkyl, having from 1 to 8carbon atoms, phenyl, naphthyl and benzyl; R is a phenyl or l-naphthylgroup; Y is a member selected from the group consisting of dimethylaminoand methoxy; m is an integer from 0 to l; R is a phenyl or naphthylgroup; Z is a 4-nitro group; and n is an integer from 0 to l.

PHOTOSENSITIVE COMPOSITIONS COMPRISING l, l DISUBSTITUTED-l,Z-DII'IYDRO-2,4-DISUBSTITUTED PHTHALAZINES where A completes a fused,mono or polynuclear aromatic ring, having six to carbon atoms; X is amember selected from the group consisting of chloro, lower alkyl, havingfrom one to four carbon atoms; and phenyl; l is a positive integer from1 to 3; R, and R are the same or different members selected from thegroup consisting of alkyl, having from one to eight carbon atoms,phenyl, naphthyl and benzyl; R is a phenyl or l-naphthyl group; Y is amember selected from the group consisting of dimethylamino and methoxy;m is O or 1; R is a phenyl or naphthyl group; Z is a 4-nitro group; andn is 0 or 1.

lt is an object of this invention to provide novel photosensi-l tivecompounds and compositions. It is a further object to pro-= vide aconvenient process for the preparation of intensely coloredazomethineimine dyes. It is a further object to provide a novelphotographic process for the formation of color images of high contrastand stability. These and other objects will become apparent from thedescription which follows.

It has now been discovered that the foregoing objects are satisfied by aphotochemical process utilizing the conversion of the l, l-disubstitutedl ,2-dihydrophthalazine compounds of Forrnulal to thecolored azomethineimine dyes of Formula ll.

The phthalazine compounds of Formula I can be conveniently prepared byfirst reacting a hydrazine compound of Formula IV with a ketosubstituted aryl carboxylic acid of Formula ill by the procedure of W.Roser, Ber., 18, 802(1885), followed by consecutive Grignard reactions.The general reaction scheme is shown below:

T-Ril-Z n XWQ III

l, l -dimethyl-l ,2dihydro-2,4-diphenylphthalazine l l -di-n-butyll,2-dihydro-2,4-di-a-naphthylphthalazine 1 l -di-n-octyll,2-dihydro-2,4-di-a-naphthylphthalazine l, l -diphenyll,2-dihydro-2-p-nitrophenyl-4-( pdimethylaminophenyl )phthalazine I l-di-a-naphthyl-l ,2-dihydro-2-(p-nitrophenyl )-4-(pmethoxyphenyl)phthalazine l l -di-B-naphthyl-l,2-dihydro-2-phenyl-4-phenylphthalazine l l -dibenzyl-l,2-dihydro-2,4-diphenylphthalazine l, l -diethyll,2-dihydro-2,4-diphenylbenzo-[ gl-phthalazine l, l -dibenzyll,2-dihydro-2-(a-naphthyl)-4-phenylbenzo- [g]-phthalazine l,l -diphenyl-l,2-dihydro-2-(p-nitrophenyl)-4-(pdimethylaminophenyl)-benzo-[h]-cinnolineSuitable aryl hydrazine compounds of Formula IV include, for example:unsubstituted phenyl or naphthyl hydrazine compounds, such as, phenylhydrazine, l-naphthyl hydrazine and IZ-naphthyl hydrazine; p-nitrophenylhydrazine and 4-nitro-lnaphthyl hydrazine.

Suitable 2-benzoylarylcarboxylic acid compounds of Formula lll include,for example: 2-benzoyl benzoic acid, 2-(anaphthoyl)benzoic acid,3-benzoyl-2-naphthoic acid, 2-(a- :naphthoyl)-2-naphthoic acid,2-benzoyl-3-chloro benzoic iacid, 2-benzoyl-2-chloro benzoic acid,2-benzoyl-4-methyl benzoic acid, 2-benzoyl-4-t-butyl benzoic acid,2-benzoyl-5- \phenyl benzoic acid, 2-benzoyl-3,4,5-triphenyl benzoicacid, l2-benzoyl-3,6-dichloro benzoic acid,2-benzoyl3,7-diemthyll-naphthoic acid, 2-benzoyl-l-naphthoic acid,l-benzoyl-2- naphthoic acid, l-benzoyl-3,7-dimethyl-2-naphthoic acid, I-benzoyl-7-methyl-2-naphthoic acid, 2-(pdimethylaminobenzoyl )benzoicacid, 2-(p-methoxybenzoyl)benzoic acid.

Suitable Grignard reagents include, for example, methyl magnesiumchloride, n-butyl magnesium chloride, n-octyl magnesium chloride, phenylmagnesium chloride, l-naphthyl magnesium chloride and benzyl magnesiumchloride.

The phthalazine compounds may be irradiated either neat in a solidstate, or dissolved, suspended or dispersed in a solvent. Preferredsolvents do not themselves adsorb ultraviolet light at the frequenciesemployed. Suitable solvents include, for example, benzene, toluene,xylene, diethylamine, pyridine, dimethylformamide and mixtures thereof.

Any source of ultraviolet radiation can generally be used in thepractice of the present invention. It is preferred to select sourceshaving frequencies which correspond to the absorption maxima of theparticular photosensitive compounds being employed. A convenient sourceof radiation is a bank of fluorescent lamps alternating in type betweensunlight phosphor lamps and blacklight fluorescent lamps. Suitable lampsinclude, for example, l5-watt Black Light, No. Fl5T8- 'BL by GeneralElectric and Rayonet Photochemical Reactor Lamps, No. RPR 3000A by TheS0. N.E. Ultraviolet Com- ,pany.

The optimum period of irradiation will naturally vary with theparticular radiation source employed, the particular compound selectedand the environment in which it is presented, among other factors.

For the purpose of imaging the activating light is patterned O by anyconventional means. Suitable means include, for example, positioningfilm transparencies or templates in which the image areas aretransparent to ultraviolet light while the backgrounds are substantiallyopaque, between the light source and photosensitive composition. Inaddition, the patterning can be achieved by means of a U.V. emittingcathode ray tube, such as, those containing P-l6 phosphors or with aU.V. laser.

The photosensitive compositions are conveniently prepared by uniformlycoating a phthalazine compound of Formula I on a conventional, absorbentphotographic substrate, such as, paper. Uniform coatings may beconveniently prepared by first dissolving the phthalazine compoundselected in a suitable organic solvent such as, acetone, benzene,toluene or tetrahydrofuran. The substrate is then immersed in thesolution and then dried at room temperature in the dark.

EXAMPLE 1 Preparation of 2,4-Diphenyll 2H )-phthalazinone A solution ofo-benzoylbenzoic acid (22.6 grams, 0.l mole)i and phenyl hydrazine (12.0grams, 0.11 mole) dissolved in: 300 ml. of 95 percent ethanol was heatedat reflux for a periodf of about 24 hours. The reaction mixture wascooled to room! temperature. The 2,4-diphenyl-l(2H)-phthalazinone formedprecipitated from solution, was collected by filtration, washed with 50ml. of ethanol and air dried to produce a crude; product (28.4 grams, 94percent yield) having a melting point? of l65-l67 C. The crude productwas purified by recrystal lization from acetic acid to produce a whitecrystalline; product having a melting point of l66-l 67 C. Preparationof l l-Dibenzyl-l ,2-dihydro-2,4-diphenylphthalazine An etherealsolution of benzyl magnesium chloride was prepared using standardprocedures by reacting magnesium (3.2 grams, 0.13 mole) with benzylchloride (22.0 grams, 0.17 mole) in 200 ml. of anhydrous ether under anitrogen atmosphere. A solution of 2,4-diphenyl-l (2H )-phthalazinone(6.0 grams, 0.021 mole) dissolved in 200 ml. of benzene was addeddropwise with stirring to the solution of benzyl magnesium chloride. Theresulting solution was refluxed on a steam bath for a period of fourhours and allowed to stand at room temperature overnight. A saturatedaqueous solution of ammonium chloride was added in sufficient quantityto decompose the remaining Grignard reagent and to dissolve themagnesium salts. The organic layer was separated, washed with water anddried over anhydrous magnesium sulfate. The solvent was removed byevaporation and the resulting oil was dissolved in ml. of benzene whichhad been heated to about 80 C. The benzene solution was diluted with 100ml. of petroleum ether. The desired product in the form of amicrocrystalline solid, pale yellow in color, was removed by filtration.Purification was effected by redissolving the solid in l5 ml. of benzenewhich had been warmed to 80C., followed by dilution with 100 ml. ofpetroleum ether. l,l-Dibenzyll ,2-. dihydro-Z,4-diphenylphthalazine inthe form of a colorless, microcrystalline solid having a melting pointof 185 C. and an elemental analysis corresponding to the empiricalformula: C H N, was obtained.

Calcd.: C, 87.93; H, 6.03; N, 6.03

Found: C, 87.99; H, 6.18; N, 6. l 2.

EXAMPLE 2 Irradiation of l l -Dibenzyl-l,2-dihydro-2,4-diphenylphthalazine l, l -Dibenzyll,2-dihydro-2,4-diphenylphthalazine (0.2 g.) was dissolved in a mixtureof benzene (50 ml.) and diethylamine (50 ml.). Nitrogen was bubbledthrough the resulting solution for a eriod of 3 minutes to removedissolved oxygen. The resu ting solution was placed in a Pyrex flask andirradiated with ultraviolet light from a high-pressure mercury vaporlamp (General Electric B-H for a period of about 5 hours. The solventwas removed by evaporation. The

remaining crystals were dissolved in 25 ml. of absolute ethanol whichwas previously cooled to about 0 C. The resulting solution was quicklyfiltered and the filtrate was evaporated to dryness to produce 0.15 g.of the crude, orange-red azomethineimine dye. Purification was effectedby recrystallization from anhydrous ether. The product,2-anilino-I,ldibenzyl-3-phenyl-l(H)-isoindolium hydroxide inner salt, inthe form of dark red crystals, had a melting point of l62-l 63 C., andthe following elemental analysis:

Calcd.: C, 87.93; H, 6.03; N, 6.03

Found: C, 87.79; H, 6.l6; N, 6.27.

EXAMPLE 3 Imaging with l, l -Dibenzyll ,2-dihydro-2,4-

diphenylphthalazine A 20 percent by weight solution of l,l-dibenzyl-l,2-dihydro-2,4-diphenylphthalazine in benzene was prepared. A sheet of 32pound white paper was immersed into the phthalazine solution and thendried at room temperature overnight in the dark.

The resulting photosensitive composition was exposed to ultravioletlight from a bank of sunlight phosphor and blacklight fluorescent lampshaving a transparency interposed between the composition and lightsource. A red-orange negative image was produced.

I claim:

I. An image-forming composition comprising a photographic substratehaving absorbed thereon a compound of the formula:

where A completes a fused, mononuclear or polynuclear aromatic ring,consisting of six to 10 carbon atoms; X is a member selected from thegroup consisting of chloro, lower alkyl, having from one to four carbonatoms, and phenyl; l is a positive integer from I to 3; R, and R are thesame or different members selected from the group consisting of alkyl,having from .one to eight carbon atoms, phenyl, naphthyl and benzyl; Ris a phenyl or l-naphthyl group; Y is a member selected from the groupconsisting of dimethylamino and methoxy; m is an integer from 0 to l; R,is a phenyl or naphthyl group; Z is a 4- nitro group; and n is aninteger from 0 to I.

2. The composition of claim 1 wherein the phthalazine compound is: l l-dibenzyll ,2-dihydro-2,4-diphenylphthalazine.

3. A photoimaging process comprising the step of forming a colored imageby irradiating a photosensitive composition of claim 1 with patternedultraviolet light.

4. The process according to claim 3 further comprising the step offixing by applying cupric chloride to the surface of the irradiatedcomposition.

5. A composition according to claim 1 wherein said aromatic ring is abenzene ring.

6. A composition according to claim 1 wherein said aromatic ring is anaphthylene ring.

2. The composition of claim 1 wherein the phthalazine compound is:1,1-dibenzyl-1,2-dihydro-2,4-diphenylphthalazine.
 3. A photoimagingprocess comprising the step of forming a colored image by irradiating aphotosensitive composition of claim 1 with patterned ultraviolet light.4. The process according to claim 3 further comprising the step offixing by applying cupric chloride to the surface of the irradiatedcomposition.
 5. A composition according to claim 1 wherein said aromaticring is a benzene ring.
 6. A composition according to claim 1 whereinsaid aromatic ring is a naphthylene ring.